Process for dyeing and printing synthetic fibers with tetra-{60 -substituted anthraquinone

ABSTRACT

An improved process for dyeing linear polyesters wherein quinizarin dyestuffs having anilino, substituted anilino or benzylamino substituents in the 5-position and the 8-position or, alternatively, having phenyl mercapto or substituted phenyl mercapto substituents in the 8-position.

United States Patent Walter Hohmann Leverkusen;

Heinrich Vollman, Leverkusen; Hans- Samuel Bien, Burscheid; Gunter Gehrke, Koeln-Flittard, all of Germany July 22, 1969 Division of Ser. No. 777,466, Nov. 20, 1968, Pat. No. 3,558,670, which is a continuation of Ser. No. 527,670, Feb. 15, 1966, abandoned Nov. 2, 1971 Farhenfabriken Bayer Aktiengesellschaft Leverkusen, Germany Feb. 19, 1965 Germany Inventors Appl. No. Filed Patented- Assignee Priority PROCESS FOR DYEING AND PRINTING SYNTHETIC FIBERS WITH TETRA-w SUBSTITUTED ANTHRAQUINONE 6 Claims, No Drawings US. Cl 8/39, 260/378, 260/380 ,4 51 lnt.Cl

[50] Field of Search [56] References Cited FOREIGN PATENTS 609,673 4/ l 962 Belgium Primary Examiner-George F. Lesmes Assistant ExaminerPatricia C. Ives Attorney-Plumley, Tyner & Sandt or substituted phenyl mercapto substituents in the 8-position.

, l,4-dihydroxy--amino-8-methylamino-anthraquinone,

PROCESS FOR DYEING AND PRINTING SYNTHETIC FIBERS WITH TETRA-a-SUBSTITUTED ANTI-IRAQUINONE This a division of application Ser. No, 777,466, filed Nov. 20, 1968, now Pat. No. 3,558,670 which, in turn, is a continuation of Ser. No. 527,502, filed Feb. 15, 1966, and now abandoned.

The present invention is concerned witH new tetra-a-substituted anthraquinone dyestuffs, with their use as dyestuffs and with the preparation thereof.

We have found that tetra-a-substituted anthraquinone derivatives of the general formula:

in which X stands for a hydroxyl or amino group, Y stands for a hydrogen, chlorine or bromine atom, R stands for a chlorine atom, an unsubstituted or substituted amino group, an acid amide radical or a mercaptan radical, and R stands for an amino group substituted by one or two hydrocarbon radicals, which may in turn be substituted, or for an acid amide or mercaptan radical, are suitable for dyeing or printing synthetic fibers.

As substituted amino groups, the dyestuffs according to the present invention may contain amino groups which are substituted by hydrocarbon radicals, and these in turn may be further substituted. The amino groups may also be substituted by one or more alkyl, aralkyl, cycloalkyl or aryl radicals. The alkyl radicals are preferably alkyl radicals containing up to six carbon atoms and may be linedwith one another via hetero atoms, as is the case, for example, in piperidino or morpholino radials. The cyclohexyl radical. is preferably used as the cycloalkyl radical and the phenyl radical as aryl radical. As substituents, the hydrocarbon radicals may contain substituents customary in anthraquinone chemistry, for example, amino groups, acylated amino groups, such as the acetylamino group; alkoxy groups, preferably those with lower alkyl radicals, such as methoxy, ethoxy or propoxy; halogen atoms, such as chlorine, bromine or fluorine; or hydroxyl groups or hydroxyalkyl groups, such as the hydroxyethyl group. The aryl or cycloalkyl radicals may also be substituted by alkyl radicals, preferably lower alkyl radicals. The acid amides are preferably -those of simple aliphatic and aromatic carboxylic acids and sulfonic acids, for example, benzamide and toluene-sulfamides. Other suitable mercaptan radicals are those substituted by hydrocarbon radicals which may contain further conventional substituents.

The following compounds are examples of dyestuffs according to the present invention: 1 4 dihydroxy-5-hydroxyethylamino-8-cyclohexylaminoanthraquinone, l,4-dihydroxy-5-amino-8-anilino-anthraquinone, 1 ,4-dihydroxy-5-tert.-butylamino-8-(4'-acetaminoanilino)-anthraquinone, l,4-dihydroxy-5-amino-8-(4'-aminoanilino)-anthraquinone, 1,4-dihydroxy-5-amino-8-(0- or -panisidino )-anthraquinone, 1,4-dihydroxy-5-amino-8-( pfluoroanilino )-anthraquinone, 1,4-dihydroxy-5-hydroxyethylamino-8-( m-chloroanilino )-anthraquinone, 1,4- dihydroxy-S -methylamino-8-( m-methoxy-p-methyl-anilino anthraquinone, l,4-dihydroxy-5-isobutylamino-8-(p-methylcyclohexylamino)-anthraquinone, l,4dihydroxy-5-diethylamino-8-p-toluidino-anthraquinone, 1,4-dihydroxy-5-amino-8 p-tert.-butylanilino )-anthraquinone, 1,4-dihydroxy-5- benzylamino-8-m-toluidino-anthraquinone, 1,4-dihydroxy-5- cyclohexylamino-8-p-toluidino-anthraquinone -p-toluidinoanthraquinone, -dihydroxy-2-chloro-5-amino-8-(p-methoxym-chloroanilino)-anthraquinone, l,4-dihydroxy 2,3-dichloro- -y-5-amino-8-naphthylamino-(2)-anthraquinone,

5,8-di-(piperidino)-anthraquinone,

' anthraquinone,

2 dihydroxy-5-(o-ethylanilino)-8-(p-chloro-anilino)- anthraquinone, l,4-dihydroxy-5-m-phenetidino-8-o-anisidinoanthraquinone, l,4-dihydroxy-5-(2,6-dimethyl-anilino)-8- 3,4-dimethyl-anilino)-anthraquinone, 1,4-dihydroxy-5- amino-S-(p-cyclohexyl-anilino)-anthraquinone, 1,4-dihydroxy-5-amino-8-(p-phenyl-anilino)-anthraquinone, 1,4-dihydrox- 1,4- dihydroxy-S,8-dianilino-anthraquinone, l ,4-dihydroxy-5 ,8-di- (o-,-mand -p-toluidino)-anthraquinone, l,4-dihydroxy-5,8- di-(p-tert.butylanilino)-anthraquinone, l,4-dihydroxy-5,8-dim-phenetidino-anthraquinone, 1,4-dihydroxy-5 ,8-di-( pchloroanilino)-anthraquinone, l,4-dihydroxy-imethylamino- 8-p-toluene-sulfanido-anthraquinone, l,4-dihydroxy-5-amino- 8-p-toluene-sulfamido-anthraquinone, 1,4-dihydroxy-5- cyclohexyl-amino-8-0-toluene-sulfamido-anthraquinone, 1,4 dihydroxy-S-anilino-8-benzamido-anthraquinone, l ,4- dihydroxy-S-anilino-8-acetylamino-anthraquinone, l ,4- dihydroxy-5-amino-8-(o-, -mand -p-methyl-phenylmercapto)-anthraquinone, l,4-dihydroxy-5-hydroxyethylamino-8- hydroxyethyl-mercapto-anthraquinone, l',4-dihydroxy-5- methylamino-8-(p-chloro-phenylmercapto)anthraquinone, 1,4-dihydroxy-5-anilino-8-thiophenoxy-anthraquinone, l ,4- dihydroxy-S-cyclohexylamino-8-(p-methyl-phenylmercaptoanthraquinone, l ,4-dihydroxy-5 anilino-8-(p-carbethoxyanilino )-anthraquinone, l,4-dihydroxy-5-amino-8-( 3 ,4- dichloroanilino )-anthraquinone, 1,4-diamino-5-hydroxyethylamino-8-chloroanthraquinone, 1,4-diamino-5 ,8-di- (hydroxyethylamino)-anthraquinone, 1,4-diamino-5-(v dimethylamino-propylamino)-8-chloroanthraquinone, 1,4- diamino-8-chloro-5-(y-trimethylamino-propylamino)- anthraquinone sulfate, l,4-diamino-5-(-y-dimethylaminopropylamino)-8-hydroxyethylamino-anthraquinone, 1,4- diamino-2,8-dichloro-5-('y -dimethylamino-propyl-amino anthraquinone, 1,4-diamino- 2,3,8-trichloro-5-anilino anthraquinone, l,4-diamino-S-thiophenylmercapto-8-anilinoanthraquinone, l,4-diamino-5-( 2 -amino-ethyl-amino )-8- hydroxy-ethylamino-anthraquinone, l,4-diamino-5,8-di-('ydimethylamino-propylamino)-anthraquinone, 1,4-diamiriol ,4 -diamino-5- morpholino-8-(v -dimethylamino-propylamino)-anthraquin- 1-amino-4-hydroxy-5-( 8 )-anilino-8-( 5 chloroanthraquinone, l-amino-4hydroxy-2-bromo-5-(8)-(-ydimethylamino-propylamino)-8-( 5 )-hydroxyethylaminoanthraquinone, 1-amino-4-hydroxy-2-chloro-5-( 8 methylamino-8-( 5 )-anilino-anthraquinone, lvamino-4- hydroxy-5-( 8 )-phenylmercapto-8-( 5 )-p-toluidino-anthraquinone, 1-hydroxy-4,5-(8)-diamino-3-bromo-8-(5)-anilinol-hydroxy-4,5-( 8 )-diamino-8-( 5 )-p-toluehesulfamido-anthraquinone, l-amino-4-hydroxy-5-(8)-(mmethyl-phenylmercapto)-8-(5 )-p-anisidino-anthraquinone, lamino-4-hydroxy-3-bromo-5,8-di-(p-toluidino)-anthraquinone and l-amino-4-hydroxy-5-(8)-methylamino-8-(5)-(pchloroanilino)-anthraquinone.

The dyestuffs. according to the present invention can be obtained by reacting 5,8-dichloro derivatives of l,4-dihydroxy-, l-amino-4-hydroxyand l,4-diamino-anthraquinone, which may also-contain-chlorine or bromine in the 2- and/or 3-positions, with ammonia or an appropriate amine, acid amide or mercaptan, the two chlorine atoms in the 5- and 8-positions being exchanged, either partially or completely, for identical or different radicals R and R of the type described above. It is possible to replace, in the first instance, only one of the chlorine atoms in the 5- and S-positions by one of the radicals R or R,. If the intermediate product thus obtained, which still contains one chlorine atom in the 5- or 8-position, is isolated and then reacted, in a second reaction, with another'of the above-mentioned reaction components, dyestuffs are obtained which have different substituents in the 5- and 8-positions.

Substantially the same dyestuffs, but with a lower content of the corresponding reaction products symmetrically substituted in the 5- and 8-positions, can also be obtained in a single reaction, that is to say without isolation of the monochloro-product in the following manner. Either the reaction component which is to be used first is used only in a slight excess over the theoretically necessary amount in the presence of a solvent, such as nitrobenzene, and the second reaction component is added only after the conversion of the first, and reacted, if necessary, at elevated temperatures; or the staring material containing two chlorine atoms in the aposition is heated directly with a mixture of two of the abovementioned reaction components. In the latter case, it is expedient to choose the proportions of the mixture in such a manner that, in the case where these compounds have a substantially different reactivity, the more inert component is present in the mixture in a correspondingly higher proportion.

The reactions can be carried out at an elevated temperature of about 50 to 220 C. and, in general, in the presence of an acid-binding agent, such as alkali metal carbonate or acetate. Inert compounds such as butanol, glycol, diglycol ethers, dimethyl formamide, chlorobenzenes or, preferably, nitrobenzene, can be used as solvents, unless reaction components added in excess act as solvents.

It is not necessary to use the dyestuffs according to the present invention in a particularly homogeneous form. It has been found, on the contrary, that mixtures of related types of dyestuffs with the general formula given above frequently have better dyeing properties than the homogeneous components of the mixture, especially in respect of the affinity and fastness to rubbing. Mixtures of this type can be prepared from the homogeneous components, for example, by dispersing them together. Dyestuff mixtures of this type can also be obtained directly in the production of the dyestuffs.

Examples of synthetic fibers to which the new dyestuffs can be applied are fiber materials based on cellulose acetate, linear polyesters, polyamides or polyacrylonitrile. The dyestuffs substituted in the lor 4-position by hydroxyl groups are preferably for dyeing and printing fiber materials based on cellulose acetate, linear polyesters or polyamides, whereas the dyestuffs substituted in the 1- and 4-positions by amino groups yield especially good results on fiber materials based on polyacrylonitrile, provided that the substituents R or R, contain solubilizing groups. The dyeing and printing of the synthetic fiber materials can be carried out by known methods. The dyestuffs can be applied, for example, without pressure with the addition of known adjuvants, i.e. so-called carriers," or under a slightly elevated pressure at temperatures of about 120 C. (HT process), or, for example, by briefly heating the materials padded or printed with the dyestufis at temperatures of 180 to 220 C. (thermosol process). The dyebaths or printing mixtures may obviously contain conventional additives. The dyeings and prints obtained have very good fastness properties, especially very good fastness to light, rubbing, sublimation and washing.

The following examples are given for the purpose of illustrating the invention, the parts being parts by weight unless otherwise stated.

EXAMPLE 1 a. parts of a fabric of synthetic polyamide are slowly heated to boiling temperature in a bath containing 400 parts, water, 0.2 part 5-amino-8-(4'-acetamino-anilino)-quinizarin in finely dispersed form and 0.2 part of a conventional dispersing agent, and dyed at the boil for 1 hour. The fabric is subsequently rinsed, optionally slightly soaped, and dried. A deep green-blue dyeing of good fastness to washing, light and rubbing is obtained.

b. The 5-amino-8-(4'-acetamino-anilino)-quinizarin can be obtained as follows:

Ammonia is introduced for about hours into a solution of parts 5,8-dichloroquinizarin in 250 parts nitrobenzene. When the reaction is completed, the crystallization product is filtered ofi with suction when cold, and washed with nitrobenzene and methanol. The S-amino-8-chloroquinizarin is obtained in a satisfactory yield. By dissolving in about 90 percent sulfuric acid and diluting the solution to an acid content of about 65 percent, the product can be obtained completely pure. Needles with a greenish metallic luster are obtained from dimethyl formamide. The color of the solution in concentrated sulfuric acid is carmine red, turning clear blue on the addition of p-formaldehyde. The color of the solution in pyridine is carmine red.

50 parts of the 5-amino-8-chloroquinizarin thus obtained, 250 parts nitrobenzene, 25 parts sodium acetate and 75 parts p-amino-acetanilide are boiled under reflux, while distilling off the acetic acid formed, until only a small amount of starting material can be detected by chromatography. The reaction mixture is diluted with 250 parts ethanol, the precipitated product is filtered off with suction at 50 C. and washed with ethanol and water. 45.6 parts 5-amino-8-(p-acetaminoani1ino)-quinizarin are obtained. The product can be pasted from sulfuric acid without hydrolysis of the acetylamino group.

EXAMPLE 2 a. If instead of pure 5-amino-8-(p-acetamino-anilino)-quinizarin, mixtures of this compound with 25-40 percent 5- amino-8-(p-amino-anilino)-quinizarin are used in example 1(a), substantially fuller, strongly bluish-green dyeings of good fastness to washing and very good fastness to light and rubbing are obtained on synthetic polyamide. Within the stated limits, the dyeing is largely independent, with regard to its shade and fastness properties, of the added amount of 5- amino-8-(p-amino-anilino)-quinizarin.

b. the dyestuff mixture stated in example 2(a) can be obtained, for example, in a single vessel process in the following manner:

60 parts 5-amino-8-chloroquinizarin obtained according to example l( b) are heated with the addition of 30 parts sodium acetate in a solution of 200 parts 4-amino-acet-anilide in 200 parts nitrobenzene at l75l80 C. for 3-4 hours. The reaction mixture is then diluted with 400 parts ethanol, the precipitated reaction product is filtered off with suction at C., washed with plenty of ethanol, extracted by stirring with dilute hydrochloric acid at 60 C., filtered off with suction, washed until neutral and dried. 71 parts 5-amino-8-(p-aminoanilino)-quinizarin containing about 25-30 percent 5-amino- 8-(p-amino-anilino)-quinizarin are obtained. c. it is also possible, however, to produce pure 5-amino-8-(pamino-ani1ino)-quinizarin according to the instruction given below and to mix this in the proportions stated in example 2(a) with the pure 5-amino-8-(p-acetamino-anilino)-quinizarin obtained according to example l(b):

20 parts 5-amino-8-chloroquinizarin, 20 parts p-phenylenediamine and 20 parts sodium acetate are heated under reflux with 200 parts nitrobenzene, until starting material can no longer be detected (about 40 minutes). The reaction mixture is allowed to cool, diluted with parts ethanol, staring at C., the precipitated reaction product is filtered off with suction at 75 C. and worked up in the manner described in example 1. 20.5 parts of 1-amino-4-(4'-amino-anilino)-5,8-dihydroxy-anthraquinone are obtained in the form of blue leaflets. The color of the solution in concentrated sulfuric acid is blue-violet, changing into a clear yellowish green on the addition of formaldehyde. When the sulfuric acid solution is poured into water, a Bordeaux-colored paste is obtained, whose shade turns green-blue upon the addition of sodium hydroxide solution. The color of the solution in pyridine is blue-green.

EXAMPLE 3 a. A fabric of polyethylene glycol terephthalate fibers is impregnated on a foulard with a liquor containing, per 1000 parts, 20 parts of finely dispersed 5-tert.butyl-amino-8-(pacetamino-anilino)-quinizarin and 10 parts of a thermosol adjuvant, especially a polyether as described, for example, in Belgian Pat. specification No. 615,102.

The fabric is then squeezed off to a weight increase of 70 percent and dried in a moving nozzle drier or drying cabinet at 80-120bL C. The fabric is subsequently treated on a stenter or nozzle hot flue with hot air at l90200 C. for about 45 seconds, then rinsed, possibly reductively after-treated, and dried. The reductive after-treatment for removing dyestuff particles superficially adhering to the fibers ca n be carried out in such a manner that the fabric is introduced at 25 C. into a bath which contains 3-5 cc./liter of a sodium hydroxide solution of 48" Be and 1-2 g./liter concentrated hydrosulfite, heating to 70 C. within about 15 minutes and keeping the bath at 70 C. for a further minutes. The fabric is subsequently rinsed while hot, acidified at 50 C. with 2-3 cc./liter of 85 percent formic acid, rinsed and dried. A clear green dyeing is obtained, which is characterizedby its high dyestuff yield and good texturing power as well as by good fastness to light, thermofixing, rubbing and washing.

A very similar dyeing is obtained, when polyester fibers from l,4-bis-hydroxymethyl-cyclohexane and terephthalic acid are dyed, instead of the polyethylene terephthalate fibers.

b. A fabric of polyethylene terephthalate fibers, previously cleaned and thermofixed, is printed with a printing paste consisting of the following components:

40 g. 5-(tert.butylamino)-8-(4'-acetaminoanilino)-quin-- izarin,

475 g. water 465 g. crystal gum l:2 and 20 g. sulfonated castor oil.

An alginate thickener may also be used, instead of crystal gum. For fixation of the dyestuff, the printed and dried material is passed over a high capacity stenter or through a condensing apparatus. The duration of the treatment is about 3060 seconds. The fixed print obtained is subsequently rinsed cold, soaped with l-2 g./liter of an anion-active detergent at 70-80 C. for about 10 minutes, rinsed first hot and then cold, and dried. A print is obtained which corresponds to the dyeing of example 3(a) and is characterized by the same good fastness properties.

c. If a fabric of triacetate is treated on a foulard with 5-tert.- butylamino-8-(p-acetamino-anilino)-quinizarin as described in example 3(a) and subsequently treated with hotair in the manner described therein, but at 220 C, then a dyeing is obtained which is slightly weaker and somewhat more bluish, but has the same good fastness properties.

(1. Polyamide fibers are dyed with 5-tert.butylamino-8-(4'- acetamino-anilino)-quinizarin according to the dyeing instructions given in example 1(a) in clear green shades of excellent fastness to light, washing and water, but only medium fastness to rubbing.

e. The dyestuff used in examples 3(a) to 3(d) is obtained as follows:

124 parts, 5,8-dichloro'quinizarin and 2L2 parts sodium carbonate are introduced into 600 parts nitrobenzene, the mixture is heated to 175 C., and 44 parts tert.-butylamine are added dropwise at this temperature, so that a slight reflux is constantly maintained. The reaction is completed after about 6-8 hours. Without isolating the resultant S-tert-butylamino- 8-chloroquinizarin, 150 parts N-acetyl-p-phenylene-diamine and 27.5 parts sodium carbonate are added to the reaction mixture which is stirred at l75-l80 C. for 12 hours. The mixture is then diluted with 1200 parts methanol, the product filtered off with suction after 2-3 hours, and washed with methanol and water.

EXAMPLE 4 a. A mixture of the product obtained according to example 3(e) with 5-tert.butylamino-8-(p-amino-anilino)-quinizarin in the ratio 3:1 dyes polyamide fibers according to the dyeing in struction of example l(a) in deep green shades of good fastness to rubbing.

b. The 5-tert.butylamino-8-(p-amino-anilino)-quinizarin can be obtained as follows:

A mixture of 17.3 parts 5-tert.butylamino-8-chloroquinizarin, 15 parts p-phenylene-diamine, 15 parts anhydrous sodium acetate and 180 parts nitrobenzene is stirred at 200-2l0 C. for 1 hour. After cooling, the reaction mixture is diluted with 350 parts methanol and 35 parts water are carefully added. The reactionproduct which crystallizes in the form of cubes is filtered off with suction, and washed with methanol and water. it dissolves in dimethyl formamide to give a solution with a bluish-green color.

EXAMPLE 5 a. 10 parts by weight of a piece of polyethylene terephthalate fabric are dyed at l20-l 30 C. for 2 hours in a bath at pH 4.5 consisting of 400 parts water and OJ part of very finely dispersed S-amino-S-anilino-quinizarin and 0.3 part of a mixture of equal parts of an aralkyl sulfonate and a nonionic polyglycol ether. After rinsing and drying, an intense, strongly greenish-blue dyeing of good fastness to light, washing, sublimation and rubbing is obtained. b. If a piece of triacetate fabric is'treated with 5-amino-8- anilino-quinizarin in the manner described in example 5(a), then a somewhat weaker greenish-blue dyeing of comparable fastness properties is obtained. c. The product employed in example 5(a) is obtained as follows:

10 parts S-amino-S-chloroquinizarin obtained according to example l(b), 70 parts aniline and seven parts sodium acetate are stirred at l70-l75 C. for 10 hours. The reaction mixture is stirred until cold, and the reaction product precipitated in the form of blue needles is filtered ofi with suction and washed with methanol and water. 10 parts S-amino-8-anilino-quinizarin are obtained.

EXAMPLE 6 a. 10 parts by weight of polyethylene terephthalate skein material are dyed in a bath adjusted to pH 4 by addition of sulfuric acid consisting of 400 parts water, 0.1 part 5-amino-8-mtoluidino-quinizarin in finely dispersed form, 3.4 parts of a mixture of o-, m-, p-cresotic acid methyl ester and 0.6 part of a mixture of equal parts of an aralkyl sulfonate and a nonionic polyglycol ether, at 96-98 C. for 2 hours, and subsequently rinsed and dried.

The fastness to rubbing can be improved by after-treating for 10-30 minutes in a gently boiling bath containing, per 1000 parts water, 5.5 parts sodium hydroxide solution of 38 Be, two parts sodium dithionite and one part of a polyglycol ether of a fatty acid amide.

b. if skein (triacetate) material is treated in the manner described in example 6(a), then a very similar, slightly weaker dyeing of comparable fastness properties is obtained.

c. The dyestuff used in example 6(a) can be prepared as follows:

10 parts 5-amino-8-chloroquinizarin obtained according to example 1(b), 70 parts m-toluidine and seven parts sodium acetate are stirred at [70-180 C. for 16 hours. Chromatography of a sample indicates only a small amount of starting material. The reaction mixture is diluted with 70 parts ethanol, the precipitated reaction product is filtered off with suction at 70 C., and washed with hot ethanol and water. 7.1 parts 5-amino-8-m-toluidino-quinizarin are obtained in the form of needles with a metallic luster, which dissolve in concentrated sulfuric acid to give a solution with a dark blue color changing to yellow-green upon addition of formaldehyde.

EXAMPLE 7 a. if instead of 5-amino-8-m-toluidino-quinizarin, the same amount of S-amino-S-o-toluidino-quinizarin is used in example 6(a), then a dyeing is obtained which is only slightly morebluish. b. The dyestuff used in example 9(a) can be obtained by reacting 5-amino-8-chloro-quinizarin with o-toluidine at l-l C. for 30 hours.

EXAMPLE 8 b. The dyestuff used in example 8(a) can be prepared as fol lows:

45 parts amino-8-chloroquinizarin and 30 parts sodium acetate are introduced into 300 parts melted p-toluidine, and the mixture is heated at l70175 C. until starting material can no longer be detected in a sample. (about 8 hours). The mixture is stirred until it has cooled to 100 C., diluted with 300 parts ethanol, suction-filtered at 60 C., washed with hot ethanol, and the filtered material extracted by boiling with dilute hydrochloric acid. 40.5 parts 5-amino-8-p-toluidinoquinizarin are obtained in the form of hexagonal blue platelets. The product dissolves in concentrated sulfuric acid to give a solution with a red color which changes to dark green with boric acid and to yellow-green with formaldehyde. The

' color of the solution in dimethyl formamide is a clear greenblue.

EXAMPLE 9 a. A fabric of polyethylene terephthalate fibers is treated with mixture of the dyestuffs obtained in examples 6(c) and 8(b) and 7(b) and 8(b), respectively, according to the dyeing instructions given in examples 5(a) and 6(a), in the proportions :75 and 75:25 percent, respectively. Deep, strongly greenish-blue dyeings of good fastness to light, washing, sublimation and rubbing are obtained. Compared with dyeings obtained with the pure dyestuffs by the same method, the dyeings thus obtained are distinguished by improved affinity, fuller shades and, in some cases also by an even better fastness to rubbing.

b. lfskein material of triacetate is dyed with the mixtures used in example 9(a), according to examples 5(b) and 6(b), then strong dyeings of comparable fastness properties are again obtained, with a somewhat more bluish shade. in this case also the mixtures yield more intense dyeings than the pure dyestuffs.

EXAMPLE 10 a. Polyethylene terephthalate is dyed with 5-amino-8-panisidino-quinizarin according to the instructions given in examples 5(a) and 6(a) in intense greenish-blue shades fast to sublimation and rubbing. b. The product used in example 10(a) is prepared as follows:

Six parts 5-amino-8-chloroquinizarin, 40 parts p-anisidine and three parts sodium acetate are stirred at l70-l 75 C. for 4 hours. The reaction mixture is diluted with 40 parts ethanol, starting at 130 C., suction-filtered at 80 C., washed with plenty of boiling ethanol, the filter cake is extracted by boiling with dilute hydrochloric acid, filtered off with suction, washed until neutral, and dried. Six parts 5-amino-8-p-anisidino-quinizarin are obtained in the form of blue needles which dissolve in concentrated sulfuric acid to give a solution with a violet color, and in borosulfuric acid to give a solution with a green color.

EXAMPLE 1 l a. Polyethylene terephthalate fibers are dyed with 5-amino-8- o-anisidino-quiniaarin according to the instructions of examples 3(a), and 5(a) and 6(a) in full green-blue shades of goodfastness to sublimation and rubbing.

b. The S-amino-8-o-anisidino-quinizarin is obtained as fol- EXAMPLE 12 a. A mixture of equal parts of the dyestuffs obtained according to examples 10(a) and ll(b) dyes triacetate material according to the dyeing examples 3(c), 5(b) and 6(b) in greenishblue shades of good fastness to sublimation and washing. b. The mixture used in example l2(a) dyes polyethylene terephthalate fibers according to the dyeing examples 5(a) and 6(a) in intense strongly greenish-blue shades of good fastness to sublimation, rubbing and washing. 0. Dyeing, which are very similar to those of examples l2(a) and l2(b) are obtained on triacetate and polyethylene terephthalate fibers, when the dyestuffs are mixed in other proportions with the limits of 20:80 to :20 percent.

EXAMPLE 13 a. Polyethylene terephthalate fibers are dyed with 5-amino-(4 -fluoro-anilino)-quinizarin according to the HT process as in example 5(a) in full greenish-blue shades of good fastness to light, sublimation and rubbing.

b, The 5-amino-8-(4'-fluoroanilino)-quinizarin was obtained as follows:

60 parts 5-amino-8-chloro-chloroquinizarin, 42 parts sodium acetate, 69 parts 4-fluoroaniline and 300 parts nitrobenzene are boiled under reflux for 20 hours. The reaction mixture is allowed to cool, the precipitated product is filtered off with suction, washed with 150 parts of nitrobenzene and subsequently with methanol, hot dilute hydrochloric acid and water. 56 parts 5-amino-8-(4'-fluoro-anilino)-quinizarin are obtained in the fonn of beautiful blue needles.

EXAMPLE 14 a. A mixture of equal parts 5-amino-8-(p-chloroanilino)-quinizarin and 5-amino-8-(m-chloroanilino)-quinizarin dyes polyester fibers according to example 5(a) and, above all 3(a), in an intense blue-green shade of very good fastness to light, washing, sublimation and rubbing. The fixation yields are very good. Compared with the dyeing obtained according to example 1 1(a), the fastness to sublimation is even better.

The compounds used in example 14(e) can be obtained according to the following instructions:

(b) 5-amino-8-(p-chloroanilino)-quinizarin:

50 parts 5-amino-8-chloroquinizarin, 300parts 4- chloroaniline and 35 parts sodium acetate are stirred at l-190 C. until only a small amount of starting material remains. Starting at C., the mixture is slowly diluted with 300 parts by volume of ethanol, suction-filtered at 80 C., and washed with hot ethanol until the discharge is clear. The filtered material is then extracted by boiling with dilute hydrochloric acid, washed until neutral, and dried. 51.7 parts S-amino-8-p-chloroanilino-quinizarin are obtained in the form of needles with a violet luster, which dissolve in concentrated sulfuric acid to give a solution with a dirty violet color, in borosulfuric acid with a blue-green color and in formaldehyde and sulfuric acid with a yellow-green color.

c. 5-amino-8-(m-chloro-anilino)-quinizarin:

50 parts 5-amino-8-chloroquinizarin, 250parts 3- chloroaniline and 35 parts sodium acetate are stirred at C. until only a small amount of starting material can be detected. The mixture is allowed to cool, covered with some 3- chloroaniline and thoroughly washed with hot methanol and water. Yield 50.1 parts S-amino-(m-chloroanilino)-quinizarin. The product dissolves in concentrated sulfuric acid to give a solution with a dirty violet color and in pyridine with a clear green-blue color.

0 EXAMPLE 15 a. Polyethylene terephthalate material is dyed with S-hydroxyethylamino-8-(p-chloroanilino)-quinizarin according to the dyeing instruction given in example 3(a) in clear, intense bluish-green shades of very good fastness to rubbing and sublimation. b. The 5-hydroxyethylamino-8-(p-chloroanilino)-quinizarin is obtained according to the following instruction:

31 parts 5,8-dichloroquinizarin are heated with 15 parts sodium acetate and 12 parts hydroxyethylamine in 120 parts nitrobenzene at 135 C. until chromatography of a sample indicates the absence of starting material (about 70 minutes). The reaction mixture is then allowed to cool to 70 C., 100 parts methanol are added with stirring, the mixture is cooled to C., the product filtered off with suction, washed with hot water and dried. 25.9 parts -hydroxyethylamino-8-chloroquinizarin are obtained in the form of needles with a red metallic luster.

34 parts of this product are heated with 30 parts sodium acetate and 100 parts p-chloroaniline at 180 C. for 30 hours, then mixed with 100 parts nitrobenzene while still hot. The mixture is then suction-filtered after cooling, and the filtrate washed with a little nitrobenzene and hot water. 24 parts 5- hydroxy-ethylamine-8-(p-chloroanilino)-quinizarin are obtained in the form of coarse needless with a metallic luster.

EXAMPLE 16 a. A polyethylene terephthalate fabric is printed according to example 3(b) with 5-amino-8-(4'-methoxy-3'-chloroanilino)- quinizarin. A blue-green print of very good fastness to sublimation is obtained. b. The product used in example 16(a) for dyeing is obtained as follows:

50parts 5-amino-8-chloroquinizarin, 200 parts 4-amino-2- chloro-anisole and 35 parts sodium acetate are stirred at 180-185 C. for about 12 hours, the mixture is subsequently diluted with 200 parts by volume ethanol, the precipitated product is filtered off with suction at 75 C. and washed in the usual manner. 56 parts S-amino-S-(p-methoxy-mchloroanilino)-quinizarin are obtained. The product dissolves in pyridine to give a solution with a clear green-blue color.

EXAMPLE 17 a. parts by weight of cellulose acetate skein material are dyed at 9698 C. for 1 hour in a bath previously adjusted to pH 5 with formic acid and containing 400 parts water, 0.2 part of the finely dispersed mixture of the dyestuffs S-hydroxyethylarnino-8-pranisidino-quinizarin and 5-hydroxyethylamino-8-o-anisidino-quinizarin in the ratio of 4:1, 3.4 parts of a mixture of o-, m-, p-cresotic acid methyl ester and 0.6 part of a mixture of equal parts of an aralkyl sulfonate and a nonionic polyglycol ether. A clear green dyeing of good fastness properties is obtained. b. The dyestuff mixture used in example l7(a) dyes polyesters according to example 6(a) and above all, according to the dyeing instructions given in examples 3(a) and 5(a), in green shades of good general fastness properties. c. The dyestuff mixture used in example l7(a) dyes polyamide according to the dyeing instruction given in example 1(a) in very fast intense green shades.

1f the pure components are used in examples l7(a)-17(c), instead of the mixtures, then weaker dyeings of a noticeably more bluish shade are obtained. 7

The compounds used in examples l7(a)-l 7(d) are obtained as follows: e. 10 parts hydroxyethylamino-8-chloroquinizarin, obtained according to example (b), are heated with 10 parts sodium acetate and 50 parts p-anisidine at 180 C. for 2 hours. After cooling to 60 C., adding 200 parts by volume methanol while stirring, filtering off with suction, washing with water and methanol, and drying, 10 parts 5-hydroxyethylamino-8-(panisidino)-duiniiarin are obtained in the form of needles with a red luster. f. 10 parts S-hydroxyethylamino-8-chloroquinizarin, obtained according to example 15(b), are heated with 10 parts sodium acetate and 50 parts o-anisidine at 180 C. for 17 hours. After working up as in example l7(e), 10 parts S-hydroxyethylamino-8-(o-anisidino)-quinizarin are obtained.

' EXAMPLE 18 a. The product which can be obtained according to paragraph (b) of the present example dyes synthetic polyamide accord-' a. 0.1 part S-hydroxyethylamino-S-methylamino-quinizarin is I pasted with 0.2 part of a 10 percent solution of Marseilles soap and made up with water at 50 C. to a volume of 300 parts with the addition of a further six parts of a solution of Marseilles soap. 10 parts acetate rayon are introduced into this bath, the temperature is raised to 75 C. within 20 minutes, the material is dyed at 75 C. for 1 hour, then rinsed with lukewarm water and dried. A clear strongly greenishblue dyeing is obtained. b. The dyestuff used in example 19(a) is obtained as follows:

Methylamine is introduced into a solution of 10 parts 5- hydroxyethylamino-8-chloroquinizarin in 50 parts nitrobenzene, first at to C. for 20 minutes, then at 150 C. for 1 hour, and finally at l60l70 C. for 1% hours.

The reaction mixture is allowed to cool and clarified with charcoal, and the filtrate diluted with a large volume of,

methanol and allowed to crystallize overnight. The product precipitated in the form of blueneedles is filtered off with suction, washed with some methanol and dried. S-hydroxyethylamino-S-methylamino-quinizarin is obtained.

EXAMPLE 20 a. A mixture of 5-n-butylamino-8-methylamino-quinizarin and 5-ibutylamino-8-methylamino-quinizarin in the ratio of 1:2 dyes polyamide fabrics according to example 1(a) in a clear blue shade of good fastness to light and satisfactory fastness to washing.

The compounds used in example 20(a) for dyeing are obtained as follows: b. 30 parts 5,8-dichloroquinizarin and 16 parts n-butylamine are stirred in 200 parts nitrobenzene at 150-160 C. for about 40 minutes. Starting at 60 C., the reaction mixture is diluted with 200 parts methanol. The product, precipitated in the form of felted needles, is filtered off with suction when cold and washed with methanol and water. 26.8 parts 5-n-butylamino-8chloroquinizarin are obtained in the form of brown-red needles with a metallic luster, which dissolve in concentrated sulfuric acid with a bluish-red color. On addition of boric acid, this solution exhibits a strong orange fluorescence.

1f the same amount of isobutylamine is used, instead of nbutylamine, then 5-isobutylamino-8-chloroquinizarin. is obtained in an analogous manner. 0. Methylamine is introduced into a solution of five parts 5- isobutylamino-S-chloro-quinizarin in 50 parts nitrobenzene at -150 C. until only traces of starting material are indicated in a sample. The reaction mixture is allowed to cool,

and diluted with 30 parts ethanol, then the precipitated reac-' tion product is filtered off with suction at 30 C. and washed with methanol and water. 3.4 parts 5-isobutylamino-8- methylamino-quinizarin are obtained in the form of blue needles.

If 5-n-butylamino-S-chloroquinizarin is used, instead of 5- isobutylamino-8-chloroquinizarin, then 5-n-butylamino-8- methylamino-quinizarin is obtained in a similar manner.

EXAMPLE 21 a. Polyamide fibers and acetate rayon are dyed according to the dyeing instructions of example 1(a) or 19(a), with 5- amino-8-methylamino-quinizarin in clear blue shades.

b. The 5-amino 8-methylamino-quinizarin is obtained as follows:

Methylamine is introduced into a solution of 15 parts amino-8-chloro-quinizarin in 100 parts nitrobenzene at 140- C. for about 6% hours. The reaction mixture is allowed to cool, and the reaction product, precipitated in the form of fine needles, is filtered off with suction and washed with methanol.

12 parts 5-amino-8-methy1amino-quinizarin are obtained in the form of blue needles which dissolve in concentrated sulfuric acid to give a solution with a Bordeaux color, and in borosulfuric acid with a green color.

EXAMPLE 22 a. When polyethylene terephthalate fibers are treated with 5- anilino-8-methylamino-quinizarin according to the dyeing instructions of examples 3( a) and 5(a), very clear green dyeings of very good fastness to sublimation are obtained.

b. The 5-anilino-8-methylamino-quinizarin is obtained as follows:

150 parts 5,8-dichloroquinizarin, 120 parts sodium acetate and 450 parts aniline are stirred at l55l60 C. until only a small amount of residual 5,8-dichloroquinizarin and, as yet not much 5,8-diani1ino-quinizarin can be detected in a chromatographed sample (about 30 minutes). Starting at 80 C., the reaction mixture is diluted with 450 parts methanol, the precipitated product filtered off with suction 60 C., washed with hot methanol, extracted by boiling with dilute hydrochloric acid, again filtered off with suction, and washed until neutral. 148 parts 5-anilino-8-chloro-quinizarin are obtained.

15 parts of the 5-anilino-8-chloroquinizarin so obtained are dissolved in 75 parts nitrobenzene and methylamine is introduced into the vigorously stirred solution until starting material is no longer present (about 3% hours). The reaction mixture is diluted with 75 parts ethanol, suction-filtered at 75 C. and worked up as above. 1 1.9 parts 5-anilino-8- methylamino-quinizarin are obtained. The product dissolves in concentrated sulfuric acid to give a solution with a Bordeaux color, turning yellow-green on addition of formaldehyde. The color of the solution in borosulfuric acid is green.

EXAMPLE 23 a. S-p-toluidino-S-dimethylamino-quinizarin dyes polyamide according to example 1(a) and polyethylene terephthalate fibers according to examples 3(a) and 5(a) in clear green shades.

b. The 5-p-toluidino-8-dimethylamino-quinizarin can be obtained as follows:

40 parts 5 ,8-dichloroquinizarin and four parts sodium acetate are introduced into 120 parts molten p-toluidine, the mixture is rapidly heated to l60-l65 C. and stirred at this temperature until only traces of 5,8-dichloro-quinizarin are detected in a sample. The reaction mixture is allowed to cool while stirring and diluting with 100 parts ethanol, starting at 100 C. at 70, the precipitated reaction product is filtered off with suction and washed with hot ethanol. The filter cake is then extracted by boiling with dilute hydrochloric acid, filtered off with suction, washed until neutral and dried. 43 parts 5-ptoludino-8chloroquinizarin of melting point 270273 C. are obtained in the form of brown-violet needles with a metallic luster. The color of the solution in concentrated sulfuric acid is violet, turning blue on addition of formaldehyde. The color o f the solution in dimethyl forrnamide is violet. V

Dimethylamine is introduced at 120 C. with vigorous stirring into a solution of eight parts of the S-p-toluidino-S- chloroquinizarin so obtained in 40 parts nitrobenzene. The reaction mixture is stirred until cold, diluted with 80 parts methanol, and the precipitated reaction product is filtered off with suction. 6.2 parts 5-p-toluidino-8-dimethylamino-quinizarin are obtained. The product dissolves in concentrated sulfuric acid with a Bordeaux color; the color turns clear blue on addition of formaldehyde.

EXAMPLE 24 a. Polyethylene terephthalate fibers are dyed with 5-ptoluidino-S-methylamino-quinizarin according to the dyeing instructions of examples 3(a), 5(a) and 6(a), in green shades fast to sublimation and rubbing and of medium fastness to light. b. The product used in example 24(a) is obtained as follows:

Methylamine is introduced into a solution of 10 parts 5-ptoluidino-8-ch1oroquinizarin in parts nitrobenzene at to C. for 2 hours and then at l45%C. for 1 hour. Starting at 60 C., the reaction mixture is diluted with 200 parts methanol and suction-filtered at 30 C. 8.7 parts 5-ptoluidino-8-methylamino-quinizarin are obtained in the form of long blue needles with a violet luster, which dissolve in concentrated sulfuric acid to give a solution with a red color turning yellow-green on addition of formaldehyde.

EXAMPLE 25 a. The product obtained according to paragraph (b) of the present example dyes polyamide fabric according to the dyeing instruction given in example 1(a) in a green shade.

b. parts 5,8-dichloroquinizarin are dissolved in 500 parts nitrobenzene and methylamine is introduced into this solution with stirring at 140150 C. until only a small amount of starting material can be detected. The reaction mixture is stirred until cold, diluted with 3.75 parts ethanol, and the product filtered off with suction at 70 C. and washed with hot alcohol. 115 parts S-methylamino-B-chloroquinizarin are obtained in the form of large blue needles with a greenish metallic luster, which dissolve in concentrated sulfuric acid to give a solution with a clear bluish-red color, and with an orange fluorescence on addition of boric acid. The flake color is violet-red, and the color ofthe solution in dimethyl forrnamide is red-violet.

20 parts of the S-methylamino-S-chloroquinizarin so obtained, 14 parts sodium acetate, 100 parts p-amino-acetanilide and 100 parts nitrobenzene are stirred at l 75 C. for 2% hours. The reaction mixture is diluted with 200 parts ethanol, and the product filtered off with suction at 80 C. and washed with ethanol, hot dilute hydrochloric acid and water. 17.4 parts 5-methylamino-8-(p-acetamino-anilino)-quinizarin are obtained in the form of black-blue needles which dissolve in concentrated sulfuric acid to give a solution with a dirty violet color, and in borosulfuric acid with a clear yellowish-green color.

EXAMPLE 26 a. A polyester fabric is dyed with 5-amino-8-(p-tert.-butylanilino)-quinizarin according to the dyeing processes of examples 3(a) and 5(a) in an intense green-blue shade fast to sublimation and light. b. The 5-amino-8-(p-tert.butyl-anilino)-quinizarin can be obtained as follows:

25 parts 5amino-8-chloroquinizarin, 17.5 parts sodium acetate and 125 parts p-tert. butyl-aniline are stirred at l80 C. for 14 hours. Starting at 120 C., the mixture is diluted with 125 parts ethanol and the precipitated reaction product filtered off with suction at 50 C. and washed with warm ethanol, dilute hydrochloric acid and water. 26.9 parts 5-amino-8-(p-tert. butyl-anilino)-quinizarin are obtained. The product dissolves in concentrated sulfuric acid to give a solution with a violet color, in borosulfuric acid with a bluishgreen color, and in a mixture of sulfuric acid and formaldehyde with a yellow-green color.

EXAMPLE 27 a. 5-hydroxyethylamino-8-p-to1uidino-quinizarin dyes the following fibers in bluish-green shades:

acetate rayon: according to dyeing example 17(a) triacetate: according to dyeing example 3(c) polyamide: according to dyeing example 1(a) and polyesters: according to dyeing examples 5(a) and 3(a).

b. The 5-hydroxyethylamino-8-p-toluidino-quinizarin is obtained as follows:

10 parts 5-hydroxyethylamino-8-chloroquinizarin, obtained according to example 15(b), are heated with 10 parts sodium acetate and 50 parts p-toluidine to C. and kept at this temperature until the color of the melt no longer changes. After cooling to 60 C., 50 parts methanol are added with stirring, and the product is filtered off with suction at 20 C. and washed with 70 percent aqueous methanol. The S-hydroxyethyl-amino-8-p-toluidino-quinizarin is obtained in good yield.

EXAMPLE 28 a. A fabric of polyethylene terephthalate fibers is treated according to the instructions of example 3(a) with 5-anilino-8-oanisidino-quinizarin. A full clear yellowish-green dyeing of very good fastness to sublimation is obtained. The good fixation yield can be still improved by carrying out the treatment with hot air at 210 C.

b. The S-anilino-8-o-anisidion-quinizarin is obtained as follows:

40 parts 5anilino-8o-anisidino-quinizarin obtained according to example 22(b), are stirred with the addition of 18 parts sodium acetate and 260 parts o-anisidine at 175-1 80 C. for 5 hours. Only traces of 5-anilino-8-chloro-quinizarin can then be detected by chromatography. Starting at 100 C., the mixture is diluted with 260 parts ethanol, and the precipitated product filtered off with suction at 70 C., washed with hot ethanol until clear and finally extracted by stirring with dilute hydrochloric acid while heating. 38 parts pure 5-anilino-8-oanisidino-quinizarin are obtained.

EXAMPLE 29 a. A polyethylene terephthalate fabric is treated according to the instruction of example 3(a) with 5-p-toluidino-8-oanisidino-quinizarin. A dyeing of very good fastness to sublimation and rubbing is obtained, which is even more yellowishgreen than that of example 24(a). b. The 5-p-toluidino-8-o-anisidino-quinizarin is prepared as follows:

l parts -p-toluidino-8-chloro-quinizarin, obtained as in example 23(b), 4.5 parts sodium acetate and 70 parts 0- anisidine are stirred at 180 C. for 5 hours. Starting at 120 C. the reaction mixture is diluted with 70 parts ethanol, and suction-filtered at 80 C. The filter cake is washed with hot ethanol until the discharge is clear, extracted at 60 C. by stirring with hydrochloric acid, and washed until neutral. parts 5 -p-toluidino-8-o-anisidino-quinizarin are obtained.

EXAMPLE 30 a. A polyethylene terephthalate fabric is dyed with 5-anilino- 8-ptoluidino-quinizarin according to the dyeing instruction of example 3(a) in a clear yellowish-green shade of good fastness to light and sublimation. Triacetate is dyed according to example 3(c) in a very clear shade which, however, is appreciably more bluish.

b. The 5-anilino-8-p-toluidino quinizarin is obtained as follows:

50 parts S-anilino-8-chloroquinizarin, obtained according to example 22(b), 10 parts sodium carbonate and 250 parts ptoluidine are stirred at l70-l 80 C. for about 2y; hours.'Starting at 120 C. the melt is subsequently diluted with 250 parts diethyleneglycol-monomethyl ether and the reaction product, precipitated in the form of beautiful green-blue needles, is filtered off with suction at 80 C., and washed with some diethyleneglycol-monomethyl ether, then with boiling methanol and water. 52.6 parts pure 5-anilino-8-p-toluidinoquinizarin are obtained.

The same product is obtained, when 50 parts S-p-toluidino- 8-chloro-quinizarin, obtained as in example 23(b), are stirred in an excess of aniline for 5 hours. Working up in the same manner yields 48.8 parts.

EXAMPLE 3] a. A polyethylene terephthalate fabric is dyed with 5-ptoluidino-8-m-toluidino-quinizarin according to the dyeing instructions of example 3( a) in a green shade fast to sublimation and light.

b. The 5-p-toluidino-8-m-toluidino-quinizarin can be obtained as follows:

20 parts p-toluidino-8-chloro-quinizarin, obtained according to example 23(b), are stirred with 7.5 parts sodium carbonate and 100 parts m-toluidine at 190-195 C. until only traces of starting material can be detected. The melt is allowed to cool down without stirring, and the precipitated reaction product filtered off with suction, washed with cold m-toluidine, ad freed from the base by steam distillation. 16.7 parts 5-ptoluidino-8-m-toluidino-quinizarinare obtained.

EXAMPLE 32 a. A fabric of polyethylene terephthalate fibers is treated according to the dyeing instructions of example 3(a) with S-mchloro-anilino-8-p-chloroanilino-quinizarin. A bluish-green dyeing of very good fastness to light and sublimation is obtained with a satisfactory fixation yield. This is substantially improved when the heat setting is carried out at 210 C. instead of at 190 C.

The product used in example 32(a) can be obtained as in examples 32(b) or 32(c); b. 20 parts 5,8-dichloroquinizarin and 20 parts sodium acetate are introduced into 100 parts molten p-chloroaniline and the mixture is stirred at 170 C. until only a small amount of dichloroquinizarin is detectable in a sample. The reaction mixture is diluted with 100 parts ethanol, and the product filtered off with suction at C., washed with hot ethanol until the discharge is violet-colored and clear, then extracted by boiling with dilute hydrochloric acid and washed until neutral. 24 parts 5-(p-chloroanilino)-8-chloroquinizarin are obtained in the form of currant-colored needles which dissolve in concentrated sulfuric acid to give a solution with a violet color, and in borosulfuric acid with a green color.

40 parts of this product, 15 parts sodium acetate and 160 parts 3-chloroaniline are stirred at l80-185 C. for l4 hours. After this interval, only a small amount of starting material can be detected. The reaction mixture is diluted with 160 parts o-dichlorobenzene, the product is filtered off with suction at 50 C., and washed with o-dichlorobenzene untilthe washings are colorless. The solvent is driven off by means of steam with the addition of hydrochloric acid, the mixture filtered, and the filtrate washed until neutral. 35.8 parts S-(pchloro-anilino)-8-(m-chloroanilino)-quinizarin are obtained. c. parts 5,8-dichloroquinizarin, 70 parts sodium acetate and 500 parts 3-chloroaniline are stirred at 185l90'C. for 2-3 hours. The reaction mixture is then stirred until cold, and diluted with 200 parts o-dichlorobenzene.Theproduct is filtered off with suction at 40 C., washed with hot methanol, extracted by boiling with dilute hydrochloric acid,-filtered off with suction, washed until neutral, and dried. 81 parts 5-(3'-' chloroanilino)-8-chloroquinizarin are obtained in the form of blue-violet needles which dissolve in sulfuric acid to give a solution with a violet color, and in borosulfuric acid with a green color.

20 parts of this product, 7.5 parts sodium acetate and 100 parts 4-chloroaniline are stirred at l80-'-l 85 C. until starting material can no longer be detected. Starting at C. the melt is diluted with lOO parts chlorobenzene. The precipitated product is filtered off with suction at 70 C., and washed with chlorobcnzene, ethanol, dilute hydrochloric acid and water. l9.5 parts of a product identical with that in 32(b) are obtained.

EXAMPLE 33 a. A fabric of polyethylene terephthalate is treated according to the dyeing instructions of example 3(a) with S-(mchloroanilino)-8-( p-fluoroanilino)-quinizarin. The dyeing obtained is very similar to that of example 32(a) but has a somewhat more bluish shade.

b. The compound used in example 33(a) is prepared as follows:

20 parts S-(m-chloroanilino)-8-chloroquinizarin, obtained according to example 32(c), eight parts sodium acetate, l00 parts nitrobenzene and 15 parts p-fluoroaniline are boiled under reflux until only traces of starting material can be detected; this is the case after about 12 hours. The reaction mixture is then worked up according to example 32(c), paragraph 2, and 21.4 parts S-(m-chloroanilino)-8-(p-fluoroanilino)- quinizarin are obtained in the form of felted needles.

EXAMPLE 34 a. A fabric of polyethylene terephthalate is treated according to the dyeing instruction of example 3 (a) with 5-o-anisidino- 8-p-anisidino-quinizarin. A clearly strongly yellowish-green l dyeing of very good fastness to sublimation is obtained.

The 5-o-anisidino-8-p-anisidino-quinizarin can be obtained in an equally high quality by the methods 34(b) and 34(c): b. 50 parts 5,8-dichloroquinizarin, 20 parts sodium acetate and 150 parts o-anisidine are stirred at 170 C. until the first l5 amount of the di-reaction product formed by the double exchange of the chlorine atoms for o-anisidine can be detected by chromatography in a sample. Starting at 1 10 C the melt is then slowly diluted with 150 parts ethanol. The precipitated reaction product is filtered off with suction at 80 C. and washed with hot ethanol until the washings are violetcolored and clear. The filtered material is subsequently briefly boiled with dilute hydrochloric acid, filtered off with suction, washed until neutral and dried. 45.8 parts are obtained.

parts of the 5-o-anisidino-8-chloroquinizarin obtained above are stirred with 7 parts sodium acetate and 100 parts panisidine at 180-185 C. until starting material can no longer be detected (about 3 hours). Starting at 100 C., the reaction mixture is then diluted with 100 parts ethyleneglycolmonomethyl ether, the product filtered off with suction at 60 C., washed successively with ethylene glycol monomethyl ether, methanol, dilute hydrochloric acid and water. After drying, 21.6 parts 5-o-anisidino-8-p-anisidino-quinizarin are obtained. c. If 200 parts p-anisidine are used in example 34(b), paragraph 1, instead of 150 parts o-anisidine, and the process is otherwise carried out as described, then 48.8 parts 5-panisidino-8-chloroquinizarin are obtained.

When this product is reacted with o-anisidine in a manner similar to that described in example 34(B), paragraph 2, the same 5-o-anisidino-S-p-anisidino-quinizarin is obtained in a somewhat poorer yield.

EXAMPLE 35 a. When a polyethylene terephthalate fabric is treated according to the dyeing instruction of example 3(a) with the following substances:

a. ophenetidino-p-phenetidino-quinizarin b. o-phenetidino-m-phenetidino-quinizarin,

c. m-phenetidino-p-phenetidino-quinizarin, but the treatment with hot air is carried out at 210 C., yellowish-green dyeings of very good fastness to sublimation are obtained. Very similar dyeings are obtained by replacing part of the phenetidines by 0- or p-anisidines in the above examples.

b. These compounds can easily be obtained with good to very good yields by methods similar to those described in examples 34(b) and 34(c).

EXAMPLE 36 a. A polyethylene terephthalate fabric is thermosolised with 5- p-anisidino-8-p-toluidino-quinizarin as in example 3(a), but at 210 C. Clear yellowish-green dyeings of good fastness to light and sublimation are obtained.

A very similar dyeing is obtained when the products obtained as in example 36(0) or 36(d) are used. b. 60 parts 5-p-anisidino-8-chloroquinizarin, obtained according to example 34(c), are stirred with 40 parts sodium acetate 175180 C. After the reaction has proceeded for about 1 hour, starting material and one-sided reaction products are no longer present in the mixture. The melt is then diluted with 300 parts diethylene glycol monomethyl ether, and suction-filtered at 5060 C. The filtered material is washed in succession with diethyleneglycol-monomethyl ether, ethanol, water, and dilute hydrochloric acid, and then again with water. After drying, there are obtained 71.3 parts of a product which is 0 shown by chromatography to consist of about 50-60 percent 5-p-toluidino-8-p-anisidino-quinizarin and 20-25 percent each of 5,8-di-p-toluidino-quinizarin and 5,8-di-p-anisidinoquinizarin.

d. 60 parts dichloroquinizarin, 40 parts sodium acetate, 36 parts p-anisidine and 200 parts p-toluidine are stirred at l75180 C. for 2% hours, then the melt is diluted with 300 parts diethyleneglycol-monomethyl ether and worked up as in example 36(c). 78.2 parts of a product are obtained, which is shown by chromatography to consist of about 50 percent 5-p- 20 toluidino-8-p-anisidino-quinizarin, about 40 percent 5,8-di-pwith regard to the amino substituents are formed can be varied to almost any extent desired, whereas the amount of asymmetrical reaction product does not change appreciably.

EXAMPLE 37 a. A fabric of polyethylene terephthalate fibers is thermosolised with 5-(m-chloro-p-methoxy-anilino)-8-mtoluidino-quinizarin as in example 3(a), but at 210C. A green dyeing of very good fastness to sublimation is obtained.

, b. The 5-(m-chloro-p-methoxy-anilino)-8-m-toluidino-quin- 'izarin was prepared as follows:

100 parts 5,8-dichloroquinizarin, 75 parts sodium acetate and 500 parts 4-amino-2-chloro-anisole are stirred at 120 C. until some di-reaction product can clearly be detected by chromatography, (about 20 minutes). Starting at 100 C., the

40 reaction mixture is diluted with 500 parts o-dichlorobenzene,

suction-filtered at 40 C., washed with o-dichlorobenzene, the filter cake is extracted by boiling with dilute hydrochloric acid, filtered off with suction and washed until neutral. 66 parts 5-(3-chloro-4-methoxy)-anilino-8-chloroquinizarin are obtained in the form of a violet crystalline powder which dissolves in concentrated sulfuric acid to give a solution with a bluish-red color, turning dark blue on addition of formaldehyde. The color of the solution in borosulfuric acid is greenish-blue.

c. parts of this product are stirred with 250 parts mtoluidine with the addition of 20 parts sodium acetate at 190 C. until starting material can no longer be detected. The melt is then diluted with 150 parts diethyleneglycol-monomethyl ether, the precipitated reaction product is filtered off with suction at C. and washed in succession with diglycol ether,

methanol and water. The filtered material is finally extracted by boiling with N-sulfuric acid, filtered off with suction washed until neutral and dried. 51 parts S-(m-chloro-pmethoxy-anilino)8-m-toluidino-quinizarin are obtained.

EXAMPLE 38 a. When a polyethylene terephthalate fabric is treated accord-- ing to the dyeing instruction of example 3(a) with 5-(2,6- dimethylanilino)-8f(3,5-dimethylanilino-quinizarin, a greenblue dyeing of good fastness to sublimation and rubbing is obtained.

Very similar dyeings are obtained, when the following products are used, instead of 5-(2,6-dimethyl-anilino)-8-(3,5- dimethylanilino)-quinizarin:

and 180 parts p-toluidine at 175l80 C. for 6 hours. Starting 5-(2,4,6-trimethylanilino)-8-(3,S-dimethylanilino)-quinat 150 C., the melt is slowly diluted with 220 parts diethyleneglycol ether. The reaction product, precipitated in i the form of large blue-black needles, is then filtered off with suction, and washed with hot methanol, hot dilute hydrochloric acid and water. 66.2 parts of product are obtained.

c. 60 parts 5,8-dichloroquinizarin, 40 parts sodium acetate,

100 parts p-anisidine and 200 parts p-toluidine are stirred at izarin,

5-( 2,6-diethyl-4-methylanilino0-8-( 3,5-dimethylanilino)- quinizann 5-( 2,4,6-trimethylanilino)-8-( 3,4-dimethylanilino)-quinizarin,

5-(2,6-dimethylanilino)-8-(3,4-dimethylanilino)quinizarin.

The compounds used in example 38(a) can be obtained, for example as follows:

b. 50 parts 5,8-dichloroquinizarin, 20 parts sodium acetate and 250 parts l-amino-2,6-dimethylbenzene are stirred at 200-210 C. until the first amount of bis-reaction product formed by the exchange of both chlorine atoms for l-amino- 2,6-dimethyl-benzene can be detected in a sample. The reaction mixture is then slowly diluted with 250 parts alcohol, and the 5-(2,6-dimethyl-anilino)-8-ehloroquinizarin, precipitated in the form red-brown needles, filtered off with suction and washed in succession with alcohol, hydrochloric acid and water. 40.2 parts are obtained.

c. If equivalent amounts of l-amino-2,4,6-trimethyl-benzene or l-amino-2,6-diethyl-4-methylbenzene are used in example 38(b), instead of l-amino-2,6-dimethylbenzene, then 5- (2,4,6-trimethylanilino)-8-chloroquinizarin and 5-(2,6- diethyl-4-methylanilino)-8-chloroquinizarin, respectively, are

obtained in the same manner.

d. 20 parts of the product obtained according to 38(b) are stirred with 9 parts sodium acetate and 100 parts 3,-5- dimethyl-aniline at 175-] 80 C. until starting material can no longer be detected. The reaction mixture is allowed to cool down, diluted with 160 parts chlorobenzene, the product precipitated in the form of blue-green needles is filtered off with suction, washed with chlorobenzene, freed from the solvent with steam, and dried. 21.1 parts 5-(2,6- dimethylanilino)-8-(3,5-dimethylanilino)-quinizarin are obtained.

e. If the same amount of 3,4-dimethylaniline is used in example 38(d), instead of 3,5-dimethylaniline, then 5-(2,6- dimethylanilino)-8-(3,4-dimethylanilino)-quinizarin is obtained, likewise in good yield.

EXAMPLE 39 a. When a polyethylene terephthalate fabric is dyed as in example 3(a) with the product obtained according to paragraph (b) of the present example, a clear, full green dyeingof very good fastness to sublimation is obtained.

b. 60 parts 5,8-dichloroquinizarin, 40 parts sodium acetate, 25 parts aniline and 200 parts nitrobenzene are stirred at 200-20 5 C. for 3 hours. Besides 90 percent 5-anilino-8-chloroquinizarin, the product then contains about 5 percent each of 5,8-. dichloroquinizarin and 5,S-dianilino-quinizarin. 75 parts panisidine are then added to the reaction mixture, which .is stirred at l95-200 C. for a further 3 hours. Starting at 140 C., the reaction mixture is then diluted with 150 parts diethyleneglycol ether, suction-filtered at 70 C., and the filtered material washed with diglycol ether, methanol, dilutej hydrochloric acid and water. 66.7 parts of a well crystallized; product are obtained, which consists of 90 percent 5-anilino-, S-p-anisidino-quinizarin and 5 percent each of 5,8-dianilinoquinizarin and 5,8-di-p-anisidino-quinizarin. These three compounds can very easily be separated from one another by the methods of thin layer chromatography.

EXAMPLE 40 a. A polyethylene terephthalate fabric is treated with the product obtained as in paragraph (b) of the present example, following the dyeing instruction of example 3(a). A green dyeing is obtained, which is very similar to that of example 39( a) and has comparable fastness properties.

b. 60 parts 5,8-dichloroquinizarin, 40 parts sodium acetate and 30 parts o-toluidine are stirred with 240 parts nitrobenzene at 195-200 C. for 2hours, a further 25 parts toluidine are then added and stirring is continued at 195-200 C. for a further 3 hours. Chromatography of a sample indicates about 6 percent starting material and already about 4 percent di-o toluidinoquinizarin. 100 parts p-anisidine are then added to the melt, which is stirred at 205 C. until monoreaction products of 5,8-dichloro-quinizarin can no longer be detected (about 4-5 hours). The melt is worked up as in example 39(b). 55 parts of a product are obtained, which consists of about 90 percent -o-toluidino-8-p-anisidino-quinizarin and about 5 percent each of di-p-anisidino-quinizarin and di-o-toluidion-quinizarin. The compounds also can be a...

separated very easily by thin layer chromatography.

EXAMPLE 41 a. a fabric of polyethylene terephthallate fibers is treated with the dyestutf mixture obtainable according to paragraph (b) of the present example following the instruction of example 3 (a), but thermosolising at 210 C. A green dyeing of good fastness to light, rubbing and sublimation is obtained. b. 60 parts 5,8-dichloroquinizarin, 40 parts sodium acetate, 25 parts p-toluidine and 300 parts p-chloroaniline are stirred at l-l85 C. for 18 hours. The reaction mixture is diluted with 200 parts diethylene glycol monomethyl ether, then suction-filtered at 70 C. The filtered material is washed with diethylene glycol ether, ethanoljdilute hydrochloric acid and water. 66 parts of a mixture are obtained, which consists of about 70 percent 5-p-toluidino-8-(p-chloroanilino)-quinizarin and about 15 percent each of 5,8-di-p-toluidino-quinizarin and 5,8-di-(p-chloroanilino)-quinizarin. These products can easily be detected side by side using thin layer chromatography.

EXAMPLE 42 a. A fabric of polyethylene terephthalate fibers is treated with the dyestuff mixture obtainable according to paragraph (b) of the present example following the instruction of example 3(a). An intense green dyeing of good fastness to light, rubbing and sublimation is obtained. I

b. 60 parts 5,8-dichloroquinizarin, 40 parts sodium acetate, 23.5 parts aniline and 300 parts p-chloroaniline are stirred at l80l85 C. for 18 hours. The mixture is worked up as described in example 41(b) and 71.8 parts of a mixture are obtained, which consists of about 70 percent 5-anilino- 8-(pchloroanilino)-quinizarin, about 20 percent 5,8-di-anilinoquinizarin and about 10 percent 5,8-di-(p-chloroanilino)- quinizarin. Also these compounds can easily be detected side by side by chromatography.

EXAMPLE 43 a. A fabric of polyethylene terephthalate fibers is dyed with 5,8-dianilino-quinizarin as in example 3(a), but treated-with hot air at 210 C. A clear green dyeing is obtained, which is characterized by good fastness to light, thermofixing, washing and rubbing. The fixation yield is almost quantitative.

b. When a triacetate fabric is treated with 5,8-dianilino-quinizarin as in example 3(a), an intense, very clear green dyeing is likewise obtained,.the shade of which however, Eappreciably more bluish.

c. The dianilino-quinizarin used in examples 43(a) and 43(b) is obtained as follows:

150 parts 5,8-dichloroquinizarin, obtained according to example 7 of British Pat. application No. 34075/64, 120 parts sodium acetate and 450 parts aniline are stirred at l65l 70 C. until no starting material and no 5-anilino-8-chloroquinizarin can be detected in a sample. This is the case after about 10 hours. Starting at 160 C., the reaction mixture is slowly diluted with 450 parts o-dichlorobenzene, suction-filtered, washed, and the solvent driven off with steam. The product is filtered off with suction and dried. 167 parts pure 5,8-dianilino-quinizarin are obtained.

EXAMPLE 44 a. A fabric of polyethylene terephthalate fibers is dyed according to example 3(a) with a liquor containing, per liter, 20 g. 5,8-di-m-toluidino-quinizarin is finally dispersed form A clear green dyeing of good fastness to rubbing, sublimation and washing is obtained. b. The 5,8-di-m-tuluidino-quinizarin is obtained as follows:

parts 5,8-dichloroquinizarin, 100 parts sodium acetate and 300 parts m-toluidine are stirred at l80-185 C. for about 12 hours and, after dilution with 300 parts diethylene glycol monomethyl ether, worked up at 75 C. as in example 3(b). parts pure 5,8-di-m-toluidino-quinizarin are obtained.

EXAMPLE 46 A fabric of polyethylene terephthalate fibers is dyed according to example 3(a) with a liquor containing, per liter, 20 g. of a mixture of equal parts 5 ,8-di-o-toluidino-quinizarin and 5,8- di-p-toludino-quinizarin. A full, clear yellowish-green dyeing of very good fastness to sublimation is obtained with a good fixation yield. This dyeing is fuller than dyeings obtained in the same way with the pure components.

EXAMPLE 47 a. A fabric of polyethylene terephthalate fibers is dyed according to example 3(a) with a liquor containing, per liter, 20 g. 5,8-di-(p-tert.-butylamino-anilino)-quinizarin. A strongly yellowish-green dyeing of good fastness to light and very good fastness to sublimation is obtained. b. The 5,8-di-(p-tert.butylamino-anilino)-quinizarin is obtained according to the following instruction:

35 parts 5,8-dichloroquinizarin obtained according to example 7 of British Pat. application No. 34075/64, 175 parts ptert.butyl-aniline in 14 parts sodium carbonate are stirred atl75 C. for 5 hours. The reaction mixture is slowly diluted with l7Sparts methanol, starting at 95 C., and a stirring is continued at 6570 C. for some time. About 20 parts water are then added dropwise, the mixture is suction-filtered at 6570 C., washed with boiling hot methanol, and the filtered material extracted by boiling with dilute hydrochloric acid, filtered off with suction, washed until neutral and dried. parts are obtained.

EXAMPLE 48 a. A fabric of polyethylene terephthalate fibers is dyed according to example 3(a) with a mixture consisting of 60 percent 5,8-di-p-anisidino-quinizarin and percent 5,8-di-oanisidino-quinizarin. A clear yellowish-green dyeing bf very good fastness to sublimation is obtained. This dyeing is substantially fuller than dyeings obtained in the same way with the pure components.

The compounds used in example 48(a) can be obtained as follows: b. 100 parts 5,8-dichloroqulnizarin, 100 parts sodium acetate and 300 parts o-anisidine are stirred at 180-l85 C. for 13 hours. The reaction mixture is then diluted with 450 parts digylcol ether and the product, precipitated in the form of blue needles, is filtered off with suction, washed in succession with diglycol ether, water, dilute hydrochloric acid and again with water, and dried. 1 15.8 parts 5,8-di-o-anisidino-quinizarin are obtained.

c. 100 parts 5,8-dichloroquinizarin, 100 parts sodium acetate and 400 parts P-anisidine are stirred at l75-l80 C. for Z'rhours and, after dilution with 500 parts diethylene glycol ether, worked as as in example 48(b). 120.7 parts 5,8-di-panisidino-quinizarin are obtained.

EXAMPLE 49 parts p-anisidine and 80 parts sodium acetate are stirred at' l80l85 C. until only traces of the asymmetric reaction product formed by the monohalogen exchange can be detected in a sample. Working up is then carried out as described in example 48(1)). 109.8 parts of a well-crystallized mixture are obtained, which consists of 5-(l-anisidino)-8-(panisidino)-quinizarin and the two products substituted symmetrically with regard to the amine.

EXAMPLE 50 a. When a polyethylene terephthalate fabric is treated with the corresponding phenetidine derivatives instead of with the anisidine derivatives used in examples 48(a) and 49(a), very similar dyeings are obtained which have a somewhat more yellowish shade, but usually have a lower color strength.

b. The 5,8-di-phenetidino-quizarins are obtained, for example, as follows:

75 parts 5,8-dichloroquinizarin are reacted in separate batches with 225 parts of each 0-, mand p-phenetidine at l-l C. with the addition to each bath of 50 parts sodium acetate. When the reaction is completed, each of the melts is diluted with 400 parts diethylene glycol monomethyl ether, suction-filtered at 75 C. and subjected to the usual washing operation. There are obtained:

94 parts 5,8-di-p-phenetidino-quinizarin (reaction time 2 hours) 94 parts 5,8-dim-phenetidino-quinizarin (reaction time 3 hours) 92 parts 5,S-di-O-phenetidino-quinizarin (reaction time 24 hours) EXAMPLE 5l a. A polyethylene terephthalate fabric is thermosolised with a mixture of equal parts of 5,8-di-(m-chloroanilino)-and 5,8-di- (p-chloroanilino-)-quinizarin according to dyeing example 3(a). A somewhat bluish-green dyeing of good fastness to light and very good fastness to sublimation is obtained. The fixation yield can be improved by a treatment with hot air at 210 C.

The compounds used in example 5 l (a) are obtained as follows:- b. 40 parts 5-(p-chloroanilino)-8-chloroquinizarin, obtained according to example 32(b), 15 parts sodium acetate and 200 pans p-chloroaniline are stirred at l80l85 C. for l3 hours. Starting at C, the mixture is slowly diluted with 200 parts o-dichlorobenzene, suction-filtcred at 80 C. The filtered material is washed, starting at 80 C., with about 300 parts 0- dichlorobenzene until the washings are clear, and freed from the solvent by steam distillation. 39.3 parts 5,8-di-(pchloroanilino)-quinizarin are obtained. c. 20 parts 5-(mchloroanilino)-8-chloroquinizarin, obtained according to example 32(c), are stirred, after the addition of7 parts sodium acetate, with I00 parts 3-chloroaniline at l80-l85 C. for l2 hours and then at 220225 C. for 6 hours. The reaction mixture is diluted with parts nitrobenzene. The product, precipitated in the form of needles, is filtered off with suction at 80 C., washed with plenty of warm nitrobenzene, and the filtered material distilled with steam. It is then treated with hot hydrochloric acid, filtered off with suction, washed until neutral and dried. 19.3 parts 5,8-di- (m-chloroanilino)-quinizarin are obtained.

EXAMPLE 52 a. A fabric of polyethylene terephthalate fibers is thermosolised according to example 3(a) at 210 C. with a liquor containing, per liter, 20 g., 5,B-di-(p-fluoroanilino)-quinizarin. A green dyeing is obtained with a somewhat more bluishshade than that of the dyeing obtained in example 5 1(a).

b. The 5,8-di-(p-fluoroanilino)-quinizarin can be obtained according to the following instruction:

75 parts 5,8-dichloroquinizarin, 50 parts sodium acetate, [25 parts p-fluoroaniline and 375 parts nitrobenzene are stirred at 2l0-2l5 C. for 14 hours. The reaction mixture is diluted with 300 parts diethylene glycol ether, suction-filtered at 70 C. and worked up in the usual manner. 93 parts of the pure product are obtained.

EXAMPLE 53 a. A fabric of polyethylene terephthalate fibers is thermosolised according to example 3(a) at 220 C. with 5,8-di- (m-chloro-p-methoxy-anilino )-quinizarin. A green dyeing of good fastness to light and sublimation is obtained. When thermosolising is carried out at 190C, only a relativelyweak dyeing is obtained.

b. the 5,8-di-(m-chloro-p-methoxy-anilino)-quinizarin is obtained as follows:-

40 parts 5,8-dichloroquinizarin, 200 parts 4-amino-2- chloroanisole and 30 parts sodium acetate are stirred at 1852190" C. for 5 hours. Initially at 120 C., the melt is then diluted with 200 parts ethanol. The product is filtered off with suction at 75 C., washed with hot ethanol until clear, and the filtered material worked up in the usual manner. 66 parts are obtained in the form of blue felted needles.

EXAMPLE 54 a. A fabric of polyethylene terephthalate fibers is treated according to example 3( a) with 5,8-di-(m-methoxy-pmethylanilino) quinizarin. A green dyeing of very good fastness to sublimation and medium fastness to rubbing is obtained. The fastness to rubbing can be improved by a reductive after-treatment as described in example 3(a).

b. The compound used in example 54(a) can be obtained as follows:

75 parts 5,8-dichloroquinizarin, obtained according to example 7 of German application F 40 552 lVb/l2qu (Le A 8300). 50 parts sodium acetate and 225 parts 4-amino-2- methoxy-l-methylbenzene are stirred at 180 C. for 6 hours.

The mixture is diluted with 200 parts diethyleglycol ether, suction-filtered at 75 C., and the filtered material worked up in the usual manner. 88 parts are obtained.

EXAMPLE 55 a. A fabric of polyethylene terephthalate fibers is treated according to example 3(a) with 5,8-di-(2,6-dimethylanilin)- quinizarin. A blue dyeing of good fastness to sublimation is obtained. b. The 5,8-di-(2,6-dimethylanilino)-quinizarin is obtained as follows: 7

50 parts 5,8 -dichloroquinizarin, 250 parts 2,6-dimethylaniline and 40 parts sodium acetate are stirred at 220-225'C. for 36 hours. The reaction mixture is stirred until cold, then suction-filtered, and the filtered material washed with 50 parts of the 2,6-dimethylaniline, 100 parts chlorobenzene, methanol and water. The filtered material is finally extracted by ln oili ng with dilute hydrochloric acid, filtered off with suction, washed until neutral and dried. 38.5 parts are obtained in pureform.

EXAMPLE 6 A fabric of polyethylene terephthalate fibers is treated according to example 3(a) with a mixture of 60percent S-amino- 8-(p-chloroanilinoyquinizarin of example 14(b) and 40percent 5,8-di- (p-chloroanilino)-quinizarin of example 51(b). A full turquoise-blue dyeing of good fastness to light and sublimation is obtained.

EXAMPLE 57 (obtained according to example 25(b)), parts ptoluene sulfamide, 38 parts potassium carbonate, 1.5 parts copper acetate, 0.5 part copper powder and 550 parts nitrobenzene is heated to 150 C. and kept at this temperature for 2 hours. When the reaction is completed, the reaction mixture is allowed to cool and diluted at 80 C. with 275 parts methanol. The reaction mixture is allowed to cool still further, and the well-crystallized reaction product filtered off with suction and washed with methanol. The filtered material is extracted by boiling with acid and dried. The 5-methylamino-8-p-t0luene sulfamide-quinizarin is obtained in a yield of 72 percent. The compound dissolves in concentrated sulfuric acid to give a solution with a red color. The color of the solution in borosulfuric acid is initially reddish-blue, but soon turn red-violet.

EXAMPLE 58 a. Polyethylene terephthalate fibers are treated according to the dyeing instruction of example 3(a) with 5-amino-8-ptoluene-sulfamido-quinizarin. A blue dyeing of very good f ast ness to sublimation is obtained.

b. A mixture of 14.5 parts 5-amino-8Chloroquinizarin, obtained according to example 1 1(b), 19 parts -p-toluene-sulfa mide, 7.6 parts potassium carbonate, 0.3 parts copper acetate and 0.1 parts copper powder is heated in 1 10 parts nitrobenzene at 150 C. for 3 hours. 55 parts methanol are added at 80 C., the mixture is suction-filtered when cold and washed with methanol until the washings are clear blue. The filter residue is brought to the boil with 200 parts water, acidified with hydrochloric acid, and washed with hot water until neutral. After drying, 17.5 parts S-amino-B-p-toluene- .sulfamido-quinizarin are obtained in the form of blue-violet prisms.

EXAMPLE 59 tained.

b. The 5-methylamino-8-phenylmercapto-quinizarin is obtained as follows:

6 parts 5-methylamino-S-chloroquinizarin, obtained as in example 25(b), are dissolved in parts dimethyl formanide and a solution of 425 parts thiophenol in 35 parts ethanol and 3.5 parts potassium hydroxide is added dropwise to this solution at 80 C. over a period of 30 minutes. Heating is continued at 80 C. for a further 30 minutes, 5 parts acetic acid are added, the mixture is diluted with 100 parts methanol, suction-filtered at 40 C. and washed with methanol and water. 7 parts S-methyl-amino-8-phenylmercapto-quinizarin are obtained in the form of violet shiny needles, which dissolve in concentrated sulfuric acid to give a blue solution turning olive-green on addition of formaldehyde.

The products listed in the following table are obtained as in example 59(b) when the reaction components of columns 4 and S of the table are used in the stoichiometric amounts corresponding to this example. When these compounds are used quinizarin.

navy-blue shades are obtained on polyester fibers according to the dyeing instructions of examples3(a) and 5(a).

EXAMPLE 73 When equal parts of 5-amino-8-(o-methyl-phenylmercapto)-quinizarin of example 65 and 1,5-dihydroxy-4,8-diamino- 3-anisyl-anthraquinone, obtained according to example 6(a) of BelgianPat. specification No. 627,010, are mixed, intense dark blue dyeings which are fast to sublimation, rubbing, washing and light are obtained on polyester fibers according to the carrier process [example 6(a)], the HT process [example 5(a)] and the thermosol process [example 3(a)].

Very similar dyeings of almost the same fastness properties are obtained, when 5-amino-8-(o-methyl-phenylmercaptoquinizarin is replaced by the same amount of 5-amino-8-(m-or p-methyl-phenylmercapto)-quinizarin.

Even more greenish dyeings can be obtained when the'percentage proportion of 1,S-dihydroxy-4,8-diamino-3-anisylantliraquinone is increased.

EXAMPLE 74 a. When a fabric of polyethylene terephthalate fibers is treated with 5-anilino-8-phenylmercapto-quinizarin according to the dyeing instructions given in example 3(a), a deep dark blue dyeing of very good fastness to rubbing, sublimation and light is obtained. b. The product used in example 74(a) is obtained as follows:

36.6 parts 5-anilinao-8-chloroquinizarin, obtained according to example 22(a), are dissolved in 370 parts dimethyl formamide and the solution is mixed at 80 C. within 30 minutes with a solution of 29 parts potassium thiophenclate in 100 parts ethanol. The reaction product is immediately precipitated from the initially clear solution in the form of blue needles. The reaction is allowed to proceed for a further minutes, then rendered weakly acidic with acetic acid. 300 parts methanol are added dropwise, and the product when cold filtered off with suction, washed with methanol and hot water, and dried. A yield of 42.3 parts is obtained.

EXAMPLE 7s a. When a polyethylene terephthalate fabric is treated with the -lates are used.

EXAMPLE 76 a. When a fabric of polyethylene terephthalate fibers is treated according to the dyeing instruction given in example 3(a) with 5-m-toluidino-8-(m-methyl-phenylmercapto)-quinizarin, a dark blue dyeing of very good general fastness properties is obtained. Very similar dyeings are obtained when S-mtoluidino-B-(oor p-methyl-phenylmercapto)qui'nizarin is used instead of 5-m-toluidino-8-(m-methyl-phenylmercapto)- b. The product used in example 76(a) is obtained as follows:

38 parts m-toluidino-8-chloroquinizarin in 300 parts dimethyl formamide are mixed at 80 C. with a solution of 31 parts of the potassium salt of m-methyl-thiophe nol in parts ethanol, the mixture is stirred for 15 minutes at the same temperature and the reaction product'isolated as described in example- 74(b). 44.2 parts 5-m-toluidino-8-( m-methyl-phenylmercapto) quinizarin are obtained. c. A completely identical reaction yields S-m-toluidino-S-(oor p-methyl-phenylmercapto)-quinizarin, also in very good yields.

EXAMPLE 77 H a. When polyamide fibers are treated with 1,4-diamino-5- hydroxyethylamino-8-chloroanthraquinone as in example l(a), an intense reddish-blue dyeing is obtained. b. The product used in example 77(a) is obtained as follows:

15 parts of cold l,4-diamino-5,8-dichloroanthraquinone is introduced into 45 parts ethanolamine. and the mixture is heated'to' 160 C. over a period of 10 minutes. The melt becomes very viscous above C. and begins to liquify again at C. As soon as the temperature begins to fall,;the mixture is again heated to 165C. for about 2 minutes and then allowed to cool. When the temperature falls to 80, 100'parts of methanol are added and'the mixture stirred until cold. The reaction product, crystallized in the form of broad needles, is filtered off with suction, washedwith' some methanol and dried. 12.7 parts of l',4-diamino-S hydroxyethyl amino-8- chloro-anthraquinone are obtained. (Tl-content 12.0 percent, m.p. l90-l92C. Dark-blue needles with a redluster, which dissolve in concentrated sulfuric acid to, give an almost colorless solution. The solution turns a clear blue on addition of formaldehyde.

EXAMPLE 78 a. When acetate rayonis treated'according to example 17(a) with l,4-diamino-5-phenylmercapto-S-chloroanthraquinone, a violet dyeing of good fastness to light and sublimation is obtained. b. The 1,4-diamino-5 phenylmercapto-B-chloroanthraquinone is obtained as follows: 1

1 1 parts 1,4 diamino-5,8-dichloroanthraquinone are dissolved in 150'parts dimethyl formamide. This solution is maintained at boiling point for 6 hours, duringwhich period a solution of 3.8 partsthiophenol in 30 parts ethanol and 3 parts potassium hydroxide is added dropwise at a constant rate. The mixture is allowed to react for a further hour; when the temperature reaches 60 C. it is diluted with 300 parts methanol and then with 250 parts water, Y suction-filtered, and thoroughly washedwith water. l,4-diamino-S-phenylmercapto-8-chloro-anthraquinone is obtained in good yield, in the form of a blue-violet crystalline powder which dissolves in concentrated sulfuric acid to give an orange-red solution turning clear blue-green with formaldehyde.

EXAMPLE 79 a. When a polyethylene terephthalate fabric is treated according to the dyeing instructions given in examples 3(a) and 5(a) with the mixture obtained as in paragraph (b) of the present example, violet dyeings of good fastness to sublimation are obtained. i

b. The product used in example 79(a) can be obtainedas follows:

2 parts 1-amino-4 hydroxy-5,8-dichloroanthraquinone are stirred with 12 parts p-toluidine at C. for 2 hours. Starting at 100 C-., the melt is then diluted with 24 parts methanol, and the precipitated reaction product filtered off with suction at 60 C., and washed with methanol, hot dilute hydrochloric acid and water. A mixture of l-amino-4-hydroxy-5-ptoluidino-8-chloroanthraquinone and 1-amino-4-hydroxy-8-ptoluidino-S-chloroanthraquinone in the form of felted violet needles is obtained in good yield.

a. When a polyethylene terephthalate fabric is treated according to the dyeing instructions of example 3(a) and (a) with the dyestuff mixture obtained as in paragraph (b) of the present example, blue-green dyeings fast to light and sublimation are obtained.

b. 9.5 parts of a mixture of 1-hydroxy-4,5-diamino-3-bromo8- chloroanthraquinone and 1-hydroxy-4,8-diamino-3-bromo-5- chloroanthraquinone, 5.3 parts sodium acetate and 50 parts ariline are heated under reflux for 30 hours. After this time, only 5 percent starting material can be detected by chromatography. The reaction mixture is allowed to cool and stirred cold for about [2 hours. The product, precipitated in the form of blue needles, is filtered off with suction, washed successively with nitrobenzene, methanol and water, and dried. 6.2 parts of a chlorine-free mixture of 1-hydroxy-4,5- diamino-3-bromo-8-anilinc-anthraquinone and 1hydr0xy-4,8-- diamino-3-bromo- S-anilinioanthraquinone are obtained. Bromine content 19.5 percent.

EXAMPLE 81 a. When a fabric of polyethylene terephthalate is dyed according to the dyeing instructions of examples 3(a) and 5(a) with the dyestuff mixture obtained as in paragraph (b) of the present example, strongly greenish-blue dyeings of good fastness to light and very good fastness to sublimation are obtained.

b. 20 parts of a mixture of 1-hydroxy-4,5-diamino-3-bromo8- chloroanthraquinone and 1-hydroxy-4,8-diamino-3-bromo-5- chloroanthraquinone, 12 parts sodium acetate and 100 parts 4-chloraniline are stirred at l90200 C. for 32 hours. Starting at 120 C., the mixture is then diluted with 100 parts nitrobenzene and the precipitated product filtered off with suction at 35 C. and washed with nitrobenzene, methanol and water. A mixture of 1hydroxy-4,5-diamino-8-(pchloroanilino)-3-bromo-anthraquinone and l-hydroxy-4,8- diamino-5-(p-chloraninlino)-3-bromo-anthraquinone is obtained in the form of beautiful blue needles.

EXAMPLE 82 a. parts polyacrylonitrile skein material are dyed at boiling temperature for one hour in a bath consisting of 400 parts water, 0.1 part 1 ,4-diamino-5-(y-dimethyl-aminopropylamino)-8-chloroanthraquinone, 0.3 parts acetic acid (30 percent) and 0.1 part sodium acetate. After rinsing and drying, an intense reddish-blue dyeing of good fastness properties is obtained.

b. The 1,4-diamino-5-('y-dimethylamino-propylamino)-8- chloroanthraquinone is obtained as follows:

30 parts 1,4-diamino-5,S-dichloroanthraquinone are heated with 180 parts y-dimethylamino-propylamine at 95-98 C. until the melt, initially viscous, has become a mobile liquid and starting material can no longer be detected by chromatography (about 5 hours). The reaction mixture is allowed to cool and slowly diluted with 500 parts water. The 1,4-diamino-5- (y-dimethyl-amino-propylamino)-8-chloroanthraquinone, precipitated in the form of beautiful needles, is filtered off with-suction, thoroughly washed with water and dried. 30 parts of a blue-violet crystalline powder are obtained. The solution in sulfuric acid is colorless, becoming deep blue on addition of formaldehyde. The color of the solution in pyridine is a clear blue.

EXAMPLE 83 a. Polyacrylonitrile is treated according to the dyeing instruction of example 82(a) with 1,4-diamino-5-chloro-8-(-ytn'methylamino-propylamino)-anthraquinone sulfate. A dyeing is obtained, which is very similar to that of example 82( a) with regard to the shade and fastness properties, but ?P 9=1 &-

b. The 1,4-diamin0-5-chloro-8-( 'y-trimethylaminopropylamino)-anthraquinone sulfate is obtained as follows:

20 parts l,4-diamino-5-chloro-8-(-y-dimethylaminopropylamino)-anthraquinone, obtained according to example 82(b), are quaternized at 70 C. with dimethyl sulfate in chlorobenzene as diluent. The precipitated quaternary salt is filtered off with suction, washed with benzene and dried. 24.5 parts are obtained.

EXAMPLE 84 a. Polyacrylonitrile skein material is treated according to the dyeing instructions of example 82(a) with 1,4diamino-5- hydroxyethylamino-8-(y-dimethylamino-propylamino)- anthraquinone. An intense greenish-blue dyeing of good general fastness properties is obtained.

b. The l,4-diamino-S-hydroxyethylamino-8-('y-dimethylamino-propylamino )-anthraquinone is obtained as follows:

20 parts l,4-diamino'5-hydroxyethylamino-8- chloroanthraquinone, obtained according to example 77(b), are heated in 60 parts y-dimethylamino-propylamine with the addition of a trace of copper acetate at 97 C. for 8 hours. The reaction mixture is stirred until cold, diluted with plenty of water, and the precipitated product filtered off with suction, washed and dried. 21 parts 1,4-diamino-5-hydroxyethylamino-8-(y-dimethylamino-propylamino)-anthraquinone are obtained in the form of a violet-blue crystalline powder. The color of the solution in concentrated sulfuric acid is pale red, turning intensely blue-violet on addition of formaldehyde. The color of the solution in pyridine is a clear blue-green.

EXAMPLE 85 a. Polyacrylonitrile is treated as in example 82(a) with the mixture obtainable according to paragraph (b) of the present example. An intense red-violet dyeing is obtained. b. 12 parts -y-dimethylamino-propylamine and 3 parts 1- amino-4-hydroxy-5,8-dichloroanthraquinone are heated on a boiling water bath for one hour. The reaction mixture is then slowly diluted with one part water, allowed to cool, and suction-filtered. A mixture of 1-amino-4-hydroxy-5-(-ydimethylamino-propylamino)-8 -chloroanthraquinone and the isomeric l-amino-4-hydroxy-5-chloro-8(y-dimethylaminopropylamino)-anthraquinone in the form of violet needles. Chlorine content 9.9 percent is obtained in good yield.

Wesl q 1. Process for dyeing or printing linear polyester fiber materials in which the dyestuff employed is an anthraquinone compound having the formula ?H (H) NH-Rg ll OH O NED-R or (I311 C) NH-Rz l OH O S-Ra in which R and R are phenyl, benzyl, or phenyl substituted with lower alkyl having one to four carbon atoms, fluoro, chloro, bromo, or carboalkoxy in which the alkoxy group contains one to four carbon atoms.

2. The process of claim 1 wherein the dyestuff has the formula 33 11 NH-R,

I H A 3 ,in which R and R are phenyl, benzyl, or phenyl substituted with lower alkyl having one to four carbon atoms, lower alkoxy having one to four carbon atoms, fluoro; chloro, bromo, amino, or carbalkoxy in which the alkoxy group contains one to four carbon atoms.

3. The process of claim 1 wherein the dyestuff has the for- I mula 5. The process of claim 1 wherein the dyestufi" has the formula | HA SQ 6. Linear polyester fihe r materials dyed by the process of claim 1. 

2. The process of claim 1 wherein the dyestuff has the formula
 3. The process of claim 1 wherein the dyestuff has the formula
 4. The process of claim 1 wherein the dyestuff has the formula
 5. The process of claim 1 wherein the dyestuff has the formula
 6. Linear polyester fiber materials dyed by the process of claim 